An apparatus for exciting the Raman spectra of gases and liquids at temperatures up to 300°C is described. For phosphorus trichloride, methyl chloride, methyl bromide, methyl alcohol, methylene chloride, methylene bromide, chloroform, and carbon tetrachloride, the Raman spectra of the gas and the liquid at the same temperature have been photographed in juxtaposition with a liquid‐prism spectrograph of speed f: 2.9 and linear dispersion 27A/mm at 4400A. The Raman spectra of gaseous n‐pentane, n‐hexane, and deuterium oxide have been photographed with 2537A excitation. The change in the Raman frequencies with the state of aggregation is different for different vibrations and varies greatly from compound to compound. In the absence of an adequate theory for this phenomenon, a search has been made for empirical regularities. The perpendicular bands of the symmetrical‐top molecules are much less diffuse in the liquid than in the gas, showing that the intermolecular forces are effective in quenching the rotation of the molecules in the liquid. The other bands are about equally sharp in gas and liquid.

The fine structure of several infra‐red absorption bands of C2H4 and C2D4 have been resolved. From the rotational constants so found, the C–C and C–H distances in this molecule were calculated to be 1.353 and 1.071A, and the H–C–H angle to be 119°55′. An assignment of fundamental frequencies has been made which is consistent with the observed data.

In the first paper of this series [J. Chem. Phys. 9, 341 (1941)], it was shown that the complex dielectric constant, ε*, of many liquid and solid dielectrics is given by a single very general formulaIn this equation ε0 and ε∞ are the ``static'' and ``infinite frequency'' dielectric constants, ω = 2π times the frequency, τ0 is a generalized relaxation time and α is a constant, 0 < α < 1. The transient current as a function of the time, t, after application of a unit constant potential difference has been calculated from this expression in series form. For times much less than τ0, the time dependence is of the form (t/τ0)−α, and for times much greater than τ0, it is of the form (t/τ0)−(2—α). The transition between these extremes occurs for the range in which t is comparable with τ0. The total absorption charge, which is the integral of the exact expression, is always finite. Although many transient data for dielectrics are of the predicted form, none have been taken over a sufficiently wide range of times adequately to test the result, nor is it yet possible to determine either the relaxation time or the static dielectric constant from available data.

The thermal decomposition of n‐butylamine proceeds in a manner analogous to that of the lower aliphatic amines. There is no evidence to support the suggestion of a molecular split into ammonia and ethylene. The mechanism appears to involve initially the production of a butylamino radical and a hydrogen atom. The butylamino radical may be the source of the ammonia found, by production of an imine whose presence is indicated. Pressure change rates yield an apparent energy of activation of 89 kcals.

The photolysis of azomethane in presence of hydrogen in the temperature range 20–200°C has been shown to yield ethane at a rate which is independent of the hydrogen. At low temperatures methane production is decreased by the presence of hydrogen but the rate increases with temperature faster than from azomethane alone. A mechanism involving CH5 has been suggested which accounts qualitatively for the observations. Essentially the same mechanism is shown to account for the decomposition of mercury dimethyl, roughly quantitatively. Strong evidence is offered that the reaction producing methane from methyl radicals and hydrogen is not CH3+H2→CH4+H. This is supported by the absence of hydrogen atoms during the azomethane photolysis studied.

On considerations of the symmetry and the approximate nature of the vibrations, the observed infra‐red and Raman frequencies of the halogen derivatives of methane are classified and their transitions in passing from one molecule to another in the series CH4–CH3X–CH2XY–CH2X2–CHX2Y–CHX3–CX4 are given. A potential function of the valence force type containing six constants is suggested for CH2X2 and the frequency equations given.

The transference numbers of sodium chloride in aqueous solution at temperatures from 15° to 45° for concentrations up to 0.1N have been determined by the moving boundary method; both anion and cation boundaries were employed. The results for 25° are in close agreement with those of Longsworth. The Longsworth function t+°′ is linear in the concentration for the more dilute range at all temperatures, thus permitting a satisfactory extrapolation to infinite dilution, but shows definite deviations from linearity for the more concentrated. The transference numbers for sodium chloride and those previously obtained for potassium chloride, combined with the conductance data reported in the accompanying paper, yield values of the ionic mobilities for the whole temperature range.

The conductance of aqueous solutions of potassium and sodium chloride has been determined at 15, 25, 35 and 45°C for concentrations from 0.0005N to 0.01N by a modified direct‐current method of high precision. At 15° and 25°, the results are in highly satisfactory agreement with the best of the existing data obtained by the a.c. bridge method. For all temperatures, the conductance can be represented within a few hundredths of a percent by the extended Onsager‐Shedlovsky equation. A calculation of the mobility of chloride ion from the conductance and the transference numbers obtained in this laboratory shows that for all temperatures the Kohlrausch rule of independent ionic mobilities is obeyed at infinite dilution within the apparent limit of error of the measurements—0.02 to 0.03 percent. The conductance and ionic mobilities for round values of the concentration, and the temperature coefficients of the ionic mobilities at infinite dilution are tabulated.

The entropy change for the stretching of rubber is calculated by statistical methods, neglecting intermolecular attractions and deformation of bonds and bond angles. The calculation involves the probability of finding the system with a given distribution of molecular configurations. An equation of state relating the tension, length, and temperature of a rubber band is then derived. Following this a discussion of the applicability and the limitations of the theory is presented.

The intensification, by nonchromophoric substitutions, of the forbidden, 1A1g→1B2U, transition in benzene is due, on the one hand, to the unsymmetrical distortion of the ring by the normal vibrations and, on the other hand, to the transition moment produced at the equilibrium position by the migration of charge from the substitution into the ring or vice versa. The latter effect is treated by the method of antisymmetrical molecular orbitals, all calculations being limited to the first order. The rules for combining transition moments due to the various groups in a polysubstituted benzene are calculated. It is shown that, for weak nonchromophoric substitutions, the intensity ratios (except for the less important variation in the normal vibrations) are for . It is further shown that if one substitutes benzene by a meta‐directing group, M, and by an orthopara‐directing group, P, of the same intensifying power, the ratios for the mono : ortho : meta : para‐derivatives should be 1 : 3 : 3 : 0. These ratios are shown to be in good qualitative agreement with experimental data.